Process for releasing fragrance

ABSTRACT

A process for releasing fragrance comprising the step of treating a) a perfume emulsified with one or more substances having emulsification actions, with b) demulsifying agent capable of demulsifying at least one of the substances having emulsification actions.

FIELD OF THE INVENTION

The present invention relates to a process for releasing fragrance, aperfume composition, a detergent composition and a process for preparingthe detergent composition.

BACKGROUND OF THE INVENTION

Conventionally, perfumes have been used for the purpose of perfumingvarious foods, detergents, cosmetics, bathing agents and the like, andthe elevation in their commercial value has been widely carried out bydeodorizing odors owned by the raw materials and releasing a fragrancecomfortable for consumers. Various methods have been so far disclosed asa perfuming method, and a direct perfuming method including the step ofspraying a perfume with a spray or the like is generally employed in thecase of, for instance, manufactured articles in the forms of powders andsolids. As other perfuming methods, for instance, Japanese PatentPublication No. 2001-521060 discloses a method including the steps ofallowing a perfume to be oil-absorbed to a certain carrier, optionallyadding a binder thereto, and compressing, extruding or the like suchmixture; Japanese Patent Laid-Open Nos. Sho 50-35072 and Hei 11-140482each discloses a method including the step of emulsifying a perfume asan oil in water containing a dissolved water-soluble matrix agent anddrying the emulsion, resulting in perfume particles encapsulated in thewater-soluble matrix.

The direct perfuming method which is the most general method isexcellent from the viewpoint of deodorization of the odors owned by rawmaterials. However, there are problems such as it is difficult toformulate a perfume having low stability against contact with asubstance contained in the composition, and the dissipation of perfumeoccurs constantly from the moment of perfuming, so that the perfume toneis lost and the fragrance has disappeared during long-term storage. Inaddition, in the method for molding a perfume disclosed in JapanesePatent Publication No. 2001-521060, the perfume is not completelyencapsulated even though there are some effects of suppressing thedissipation of perfume to a certain extent, so that the perfuming methodhas not yet been attained to a level sufficient to keep the perfumestable for long-term storage.

On the other hand, in the techniques disclosed in Japanese PatentLaid-Open Nos. Sho 50-35072 and Hei 11-140482, it is considered thatperfume particles retain perfume in a water-soluble matrix in the formof a capsule, thereby providing high storage stability. However, since astable emulsion durable in the emulsification and drying steps isnecessary so that the perfume is present in the form of an emulsionprepared in the emulsification step, there are some problems such as thefragrance is released in a lower amount during dissolution whendissolved during use, and the ability to sustain a fragrance for acertain object is lowered when the object is perfumed by such anoperation. Consequently, there is a defect that the property owned bythe perfume itself cannot be satisfactorily exhibited.

SUMMARY OF THE INVENTION

The present invention relates to:

[1] a process for releasing perfume including the step of treating

-   a) a perfume emulsified with one or more substances having    emulsification actions, with-   b) a demulsifying agent capable of demulsifying at least one of the    substances having emulsification actions;    [2] a perfume composition containing:-   a) a perfume emulsified with one or more substances having    emulsification actions, and-   b) a demulsifying agent capable of demulsifying at least one of the    substances having emulsification actions;    [3] a detergent composition containing the above perfume    composition; and    [4] a process for preparing a detergent composition including the    step of carrying out direct perfuming to the above perfume    composition or the above detergent composition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a SEM image of a cross section of perfume particle 6obtained in the Example, wherein pores observed on the cross sectionshow oil droplets of a perfume, from which it can be seen that a largenumber of oil droplets are dispersed in the perfume particles.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a process for releasing fragrance, aperfume composition, a detergent composition and a process for preparingthe detergent composition, which, for instance, suppress dissipation ofperfume before use, are excellent in a long-term storage stability, andallow the properties of a perfume to be satisfactorily exhibited uponuse.

As a result of intensive studies, the present inventors have found thatin a technique of encapsulating perfume in a water-soluble matrix, acombination of a substance having a certain kind of emulsificationaction with a demulsifying agent allows the properties of the perfumeitself to be satisfactorily exhibited upon use, while suppressing thedissipation before use. The present invention has been perfectedthereby.

Therefore, by using the process for releasing fragrance of the presentinvention, some effects that powders, solid manufactured articles or thelike for, for instance, detergents, bathing agents, foods, beverages andthe like, can be produced, which, for instance, suppress the dissipationof perfume before use, have excellent long-term storage stability, andmoreover allow the properties of a perfume to be sufficiently exhibitedupon use, are exhibited.

One feature of the process for releasing a fragrance of the presentinvention resides in that the process includes the step of treating aperfume (hereinafter also referred to as component a)) emulsified withone or more substances having emulsification actions (hereinafter simplyreferred to as an emulsification action substance), with a demulsifyingagent (hereinafter also referred to as component b)) for demulsifying atleast one of the emulsification action substances.

By using the process for releasing a fragrance of the present inventionhaving the above feature, excellent effects are exhibited such as thedissipation of a perfume before use is suppressed, long-term storagestability of the perfume is excellent, and moreover the properties ofthe perfume can be sufficiently exhibited upon use.

Particularly, in the present invention, by using a combination of anemulsification action substance with a demulsifying agent fordemulsifying the emulsification action substance, effects are exhibitedsuch as a perfume is released upon use while maintaining stabilitydurable for the emulsification and drying steps, potential of theperfume itself can be satisfactorily exhibited, and perfuming withsuppressed dissipation during storage can be realized.

Further, according to the present invention, the formulation of acertain perfume which has been difficult to formulate using conventionaltechniques from the viewpoint of stability, and the increase in theupper limit of the perfume formulation amount which has been limitedfrom the viewpoint of bleed-out property and the like can be realized.Also, a system for releasing fragrance which has not so far been found,which is capable of changing the state of powders and solids before use,generation of fragrance upon use, perfume tone of the remainingfragrance on an object and its strength can be realized by combining thepresent invention with a known perfuming method.

The present invention will be described in detail hereinbelow.

[Component a)]

In the present invention, as component a), a perfume emulsified with oneor more emulsification action substances is used.

The process for releasing fragrance of the present invention can be usedin various industrial fields. Among them, the process is preferably usedin the fields of various foods, detergents, cosmetics and bathing agentsin which demand for perfume is high. Especially, the process is suitablyused in the field of detergents from the viewpoint of the existence of avariety of usable kinds of perfume.

The emulsification action substance usable in the present invention isnot particularly limited, and includes any emulsifying agents and thelike. When one kind of the emulsification action substance is used inthe composition of the present invention, the emulsification actionsubstance is required to be a substance having an agent (demulsifyingagent) for demulsifying the emulsification action substance in its anemulsification system. On the other hand, when two or moreemulsification action substances are used in the composition of thepresent invention, it is necessary that at least one emulsificationaction substance having the corresponding demulsifying agent iscontained.

Here, the emulsification action substance involves any substancescapable of forming an emulsion state (showing a state of forming arelatively stable system in which in two liquids not easily dissolvedinto each other, one constitutes a continuous phase and the otherconstitutes a dispersed phase in the form of fine particles), inaddition to general emulsifying agents.

Examples of the emulsification action substance include cellulose-basedemulsification action substances demulsified with cellulase such ascationated celluloses, methyl cellulose, carboxymethyl cellulose, metalsalts thereof and hydroxypropylmethyl cellulose; protein-basedemulsification action substances demulsified with protease such assodium salt of casein, milk protein and soybean protein; starch-basedemulsification action substances demulsified with amylase such ascationated starches, esterified processed starches such asoctenylsuccinate starch and sucrose fatty acid esters; emulsificationaction substances demulsified by pH adjustment with an alkali or anacid, or changing salt strength with an electrolyte or the like, such aspolyoxyalkylene-based nonionic surfactants, and sucrose fatty acidesters. Particularly, when used for a detergent composition formulation,cellulose-based and protein-based emulsification action substancesdemulsified with an enzyme or an alkali having a deterging action areadvantageous, since the enzyme or the alkali used together as ademulsifying agent can also exhibit a deterging action. Among them,cationated celluloses, methyl cellulose and sodium salt of casein andthe like are preferable. These emulsification action substances can beused alone or in combination of two or more. In the present invention,when two or more emulsification action substances are used, acombination thereof is not particularly limited, so long as one or moreemulsification action substances to be demulsified with a demulsifyingagent described later are contained.

The amount of the emulsification action substance used varies dependingon the kinds and amounts of perfume to be added, the kinds of theemulsification action substance and the like. The amount is notparticularly limited, so long as a stable emulsion being durable for theemulsification and drying steps is obtained. The typical amount used ispreferably from 0.001 to 1 part by weight, more preferably from 0.01 to0.5 part by weight, based on 1 part by weight of a perfume describedlater. When two or more kinds of the emulsification action substancesare used, the amount of the emulsification action substance used to bedemulsified is preferably 10% by weight or more, more preferably 50% byweight or more of all of the emulsification action substances.

In component a) used in the present invention, the state of the perfumeemulsified with the above emulsification action substance is notparticularly limited. Particularly, it is preferable to disperse andimmobilize a perfume in the form of an oil droplet with the aboveemulsification action substance to form perfume particles and to use theperfume particles as component a), from the viewpoints of suppression ofthe dissipation before use and its excellent long-term storagestability.

In the present invention, the term “dispersing and immobilizing” refersto a state in which oil droplets are immobilized in the form of fineliquid droplets in a matrix formed by a compound forming matrix.

As the perfume which can be used in the present invention, any compoundscan be used depending on its purpose. The perfume includes, forinstance, natural perfumes, synthetic perfumes and mixed perfumesobtained by mixing the natural perfumes and the synthetic perfumes.These may contain components other than perfumes, such as a solvent.

For instance, when the present invention is used for a powder detergent,the perfume includes natural perfumes such as grapefruit oil, rose oil,and aroma oil, synthetic perfumes such as limonene, menthol,citronellol, jasmone, and pentalide, mixed perfumes prepared by mixingthe natural perfumes and the synthetic perfumes, and the like.

The amount of the perfume in component a) is preferably from 5 to 70% byweight, more preferably from 10 to 50% by weight, from the viewpoints ofsuppression of the dissipation, improvement in the immobilization ratioand decrease in the preparation costs.

In addition, when component a) is prepared, it is preferable to add amatrix-forming agent as a compound for dispersing and immobilizing aperfume in the form of an oil droplet. As the matrix-forming agent, anycompound can be used so long as the compound is a substance which iswater soluble and has a matrix-forming ability. The matrix-forming agentincludes processed starches, modified starches, gelatin-degradedsubstances, agar, sodium salt of carboxymethyl cellulose and the like.Among them, dextrin and hydrolyzed dextrin such as maltodextrin, andstarch derivatives such as esterified starches and etherified starchesare preferable from the viewpoint of the density of the matrix formed.When a hydrolyzed starch is used, the lower the degree of hydrolysis, DEvalue, the better since the encapsulated state becomes favorablyexcellent. However, ones having a lower DE value tend to show lowersolubility, so that it is necessary to adjust the DE value dependingupon the desired solubility for a perfume composition. Therefore, a DEvalue of from 5 to 15 is preferable, giving an excellent balance betweenencapsulation property and solubility.

The above emulsification action substance may function as amatrix-forming agent, and the matrix-forming agent may function as theabove emulsification action substance, so that they perform an overlapin their functions, in some cases.

The amount of the matrix-forming agent in component a) is preferablyfrom 10 to 90% by weight, more preferably from 20 to 80% by weight, fromthe viewpoints of suppression of the dissipation, improvement in theimmobilization ratio and decrease in the preparation costs.

In addition, optional components which may be contained in component a)include film strength-controlling agents such as polyhydric alcohols,saccharides and carrageenan, and colorants such as pigments and dyes.

The amount of these optional components in component a) is preferablyfrom 0 to 20% by weight, more preferably from 0 to 10% by weight fromthe viewpoint of not hindering the matrix formation.

It is preferable that the perfume particles having the composition asdescribed above [component a)] are obtained in the form of powder byemulsifying a perfume with an emulsification action substance, andthereafter drying the emulsion, from the viewpoints of productivity anduniformity of the composition. The preferred preparation process is, forinstance, a process including the following steps, without intending tolimit the present invention to this process.

(1) Emulsification Step

The above matrix-forming agent is dispersed or dissolved in water whichis appropriately temperature-controlled, an emulsification actionsubstance and a perfume are added thereto, and the mixture is emulsifiedwith a known means such as a homomixer or a line mixer, to form anemulsion.

(2) Drying Step

Next, the emulsion obtained is spray-dried by a known means, resultingin perfume particles in which perfume components are encapsulated in awater-soluble matrix.

(3) Processing Step (Optional Step)

The resulting perfume particles can also be subjected to a secondaryprocess according to its purposes. The secondary process includes, forinstance, removal of fine powders and coarse granules by sieving,processing of particle size and shape by a granulation and moldingprocedures, coloration with pigments and dyes, and the like.

The shape and size of the perfume particles obtained by the aboveprocess (after the drying step) are not particularly limited, and itssize (average particle size) is preferably from 10 to 5000 μm, morepreferably from 100 to 1000 μm, from the viewpoints of treatmentcapacity in the drying step and handling property of the resultingparticles.

The median diameter measured by a laser diffraction/scattering typeparticle size distribution analyzer LA-920 (commercially available fromHORIBA, Ltd.) is used as an average powder particle size (particle sizeof the perfume particles after the drying step) or an average particlesize of the emulsified perfume (particle size of emulsified perfumebefore the drying step). As the dispersion medium, ethanol is used forthe determination of a powder particle size, and water is used for thedetermination of a particle size of the emulsified perfume.

In the case of the determination of the particle size of the emulsifiedperfume, the emulsified perfume is adjusted to a given concentration,and thereafter the emulsified dispersion diameter is determined. In thecase of the determination of a powder particle size, the powder isirradiated with an ultrasonic wave of intermediate level (specifically,4 of 7 stages of the analyzer LA-920) for 1 minute, and the dispersiondiameter is determined. When the powder particle size determined withLA-920 is 100 μm or more, the determination is carried out by a Ro-Tapmethod.

[Component b)]

In the process for releasing fragrance of the present invention,component a) is treated with a demulsifying agent [component b)] asdescribed above. In the present invention, by using component b), thereis an advantage of satisfying two requirements, which are usuallyincompatible to each other, of obtaining a stable emulsified perfumedurable for preparation in the emulsification and drying steps, andefficiently releasing a perfume during use.

The demulsifying agent usable in the present invention refers to anagent having an action of demulsifying at least one of theemulsification action substances in the above component a). Examples ofthe demulsifying agent include enzymes, alkalis, acids, electrolytes andthe like, and at least one member selected from the group consisting ofthese demulsifying agents is suitably used. The enzyme includescellulase, protease, amylase, lipase and the like. The alkali includessodium carbonate, potassium carbonate, sodium hydroxide, potassiumhydroxide and the like. The acid includes succinic acid, fumaric acid,phthalic acid, citric acid and the like. The electrolyte includes sodiumsulfate, sodium chloride and the like in addition to the above alkalis.Among them, the enzymes are preferable, and cellulase and protease aremore preferable from the viewpoint of obtaining a demulsification effectby addition in a small amount. These components b) may be used alone orin combination of two or more.

In the present invention, in the case of a powder detergent which is apreferred embodiment, whether or not component b) has a demulsificationaction is judged according to a method described in the Examples setforth below. In the case of products other than powder detergents,component b) may be used in an appropriate amount in place of enzymesdescribed later.

The preferable combination of component b) and an emulsification actionsubstance to be demulsified by component b) includes cationatedcellulose or methyl cellulose when component b) is cellulase; sodiumsalt of casein when component b) is protease; an esterified processedstarch or a sucrose fatty ester when component b) is amylase; and sodiumsalt of casein or a sucrose fatty ester when component b) is an alkali,depending upon the structure and feature of the emulsification actionsubstance. Among them, it is preferable that component b) is cellulaseand the emulsification action substance is cationated cellulose ormethyl cellulose, or that component b) is protease and theemulsification action substance is sodium salt of casein.

It is necessary that the amount of component b) is a concentrationrequired for the demulsification of the emulsification action substancein component a) upon use. The optimum range thereof varies depending onthe use embodiment (concentration, time and the like) of themanufactured articles, the strength of an emulsion constitutingcomponent a), and the demulsification abilities (enzymatic activity,dissociation strength and the like) of component b). Samples havingchanged formulation amounts of component b) may be actually prepared,and the desired formulation amount can be determined by the sensoryevaluation based on the generation of fragrance during dissolution,fragrance-keeping property and the like. For instance, in the case of apowder detergent which is a preferred embodiment of the presentinvention, a detergent is usually used in an amount of 20 to 40 g to 5to 30 L of water (0.6 to 8 g/L). For instance, when sodium salt ofcasein, which is a protein-based emulsifying agent degraded anddemulsified with protease, is used as an emulsification action substanceand KAP13.1B (trade name, commercially available from Kao Corporation),which is a protease granule, is used as a demulsifying agent, it ispreferable that the demulsifying agent is used in an amount of from 10to 10000 parts by weight, more preferably from 100 to 1000 parts byweight based on 100 parts by weight of the emulsification actionsubstance in the detergent, and the emulsification action substance istreated with the demulsifying agent in water.

In addition, in the present invention, “treating component a) withcomponent b)” refers to generating a situation in which component a) andcomponent b) are substantially contacted with each other so thatcomponent b) affects component a). The process includes, for instance, aprocess including the step of dissolving both component a) and componentb) in a medium such as water; a process including the step ofpenetrating component a) with component b) in the form of a gas or aliquid in a case where component a) is in the form of a solid; and thelike. In the case where both component a) and component b) are in theform of a solid such as a powder and there is substantially nopossibility of demulsification taking place during storage when bothcomponents are combined, the process includes a process including thesteps of previously blending both of the components into a singlecomposition containing component a) and component b), and dissolving thecomposition in an appropriate medium upon use. Usually, the process ofmaking the components into a single composition is a preferred processfor use, from the viewpoint of easy handling. Among the embodimentsmentioned above, an even more preferable application example is alaundry powder detergent. Since the feature of the present inventionresides in that the perfume is efficiently released to generatefragrance when dissolved in water, the more preferable embodiment is apowder detergent used mainly for hand-washing laundry. For instance,when the feature is used to generate fragrance during hand-washinglaundry, use of a highly volatile perfume such as limonene as theperfume is very preferable, since fragrance generation is quicklyobtained.

One of the main features of the present invention resides in theconversion of the state of perfume from an emulsified state into a freestate in a situation where fragrance is exhibited. By carrying out thisconversion, two functions, which are usually incompatible to each other,of maintaining a stable storage state without losing perfume by amechanism such as dissipation or degradation during preparation andstorage, and efficient generation or releasing of perfume during use canbe both satisfied.

The perfume in an emulsified state has been known to have a lowdissipation rate to an upper surface of the liquid. In the case of apowder detergent, adsorption of a perfume to a spin-dried cloth duringwashing is considered to be caused by hydrophobic adsorption accordingto the hydrophobicity of the perfume. Because of these mechanisms, whena perfume is in a stable emulsified state even when used, water isundesirably drained while the perfume components remain dispersed inwater, thereby increasing the amount of the perfume components usedineffectively. As a result, problems such as a decrease in fragrance inuse, and decrease in fragrance remaining on the spin-dried cloth mayoccur. Therefore, the present invention solves the problems as describedabove by treating an emulsified perfume with a demulsifying agent induring use, thereby positively breaking up the emulsified state of theemulsified perfume.

By using the process for releasing fragrance of the present inventionhaving the constitution as described above as a perfuming method,manufactured articles such as various foods, detergents, cosmetics, andbathing agents each having storage stability for the fragrance and ahigher degree of freedom in the selection of fragrances, and beingexcellent in perfume generation and perfume-keeping property upon usecan be obtained.

In addition, the perfume composition of the present invention containsthe above component a) and the above component b). The kinds and amountratio of component a) and component b) may be the same as thosedescribed above.

The total content of component a) and component b) in the perfumecomposition of the present invention is preferably from 0.1 to 20% byweight, more preferably from 1 to 5% by weight from the viewpoint of thebalance between functions inherently owned by the manufactured articleand improvement in added values from the aspect of fragrance.

The perfume composition of the present invention may contain optionalcomponents depending upon its purpose of using the perfume composition.The above purpose includes, for instance, detergents such as powderdetergents, bathing agents, foods such as powder soup and gum, cosmeticsand the like, among which the detergents are preferable. The presentinvention also encompasses a detergent composition which is oneembodiment of the perfume composition of the present invention. It ispreferable that the perfume composition of the present invention is apowder or solid manufactured article such as a detergent, a solidbathing agent, a food or a beverage because its method of use mayinclude the step of dissolving a powdery manufactured article upon use.

When the perfume composition of the present invention is used for adetergent composition, it is preferable that the detergent compositionfurther contains one or more compounds selected from the groupconsisting of surfactants, alkalizing agents, water softening agents,polymers and enzymes as optional components.

The above demulsifying agent may serve as an optional component, and theoptional component may serve as the demulsifying agent, so that theyshow an overlap in their functions in some cases.

The surfactant includes nonionic surfactants such as polyoxyalkylenealkyl (phenyl) ethers, and alkyl(polyalkylene) polyglycosides, anionicsurfactants such as sulfuric acid esters of alcohols andalkylbenzenesulfonates, and, known surfactants usually used indetergents, such as cationic surfactants and amphoteric surfactants.

The alkalizing agent includes sodium carbonate, potassium carbonate,sodium hydrogencarbonate, sodium hydrogensulfate and the like.

The water softening agent includes zeolite, citrates, tripolyphosphates,amorphous silica derivatives, crystalline silicate compounds and thelike.

The polymer includes acrylic acid polymers, acrylic acid-maleic acidcopolymers, anti-redeposition agents such as carboxymethyl cellulose,and the like.

The enzyme includes alkali cellulases, alkali proteases, amylases,lipases, keratinases, esterases, cutinases and the like.

In addition, the above detergent composition may contain a dispersant, adefoaming agent, a salt strength-controlling agent, a cloth softeningagent, a bleaching agent, a bleach activator, a fluorescent whiteningagent or the like.

The total content of these optional components is preferably from 80 to99.9% by weight, more preferably 95 to 99% by weight of the detergentcomposition from the viewpoint of obtaining a sufficient detergingaction.

The perfume composition and the detergent composition of the presentinvention can be each prepared by adding and mixing the above componenta), component b) and the above optional components when necessary by aknown method.

In addition, the present invention has an advantage that the selectionof fragrance design can be increased by carrying out direct perfuming orusing a perfume-penetrated molded product to the above perfumecomposition, the above detergent composition, or in the above processfor releasing fragrance according to the purposes for the manufacturedarticles to be manufactured, for instance, for the purpose ofdeodorizing the odor of a base material, and the like. Therefore, thepresent invention also provides a process for preparing a detergentcomposition including the step of carrying out direct perfuming to theabove perfume composition or the above detergent composition.

Examples of the direct perfuming method include a process including thestep of mixing component a), component b) and optional components by aknown method with a perfume sprayed thereto by means of a spray or thelike.

EXAMPLES

The present invention will be described in further detail by means ofthe following examples, without intending to limit the scope of thepresent invention thereto.

(Evaluation Conditions)

Here, as to the judgment on whether or not the combination can bedemulsified, it is difficult to prove the occurrence of ademulsification phenomenon in the form of an embodiment itself since theamount of the perfume formulated is usually 1% by weight or less, andthe perfume has a very low concentration of several dozen ppm in adissolution state upon use. Therefore, it is advantageous toappropriately concentrate main components including the perfumeparticles and components which are considered to be involved indemulsification of the perfume particles in the composition(specifically, materials which hinder the visual judgment, such aswater-insoluble components, are not formulated), whereby thedemulsification can be judged conveniently. Therefore, the method ofjudging the demulsification in the present invention will be describedhereinbelow, and the results are described in each of the Examples andComparative Examples.

(Method of Judging Demulsification)

In each of two 200-mL beakers, 100 g of an emulsion was prepared in aconcentration of 0.05% by weight calculated as a perfume (theconcentration being adjusted by adding water to the emulsion or perfumeparticles before spray-drying), and likewise in two 200 mL beakers, 100g of water was furnished. The water temperature for each of theabove-mentioned four beakers was controlled at 20° C., and water wasstirred with a stirrer having a length of 30 mm, to an extent that adepth of swirl of half that of the liquid depth was formed. Ademulsifying agent to be judged was supplied in a given amount into oneof the emulsion-containing beakers and one of the water-containingbeakers (Here, components other than the demulsifying agent weresupplied as little as possible in order to prevent disturbance onabsorbance since the extent of demulsification is determined byabsorbance. In addition, although it is necessary to adjust thesupplying amount depending on the concentration assumed in the actualmanufactured article system, and the mechanism for demulsification, thesupplying amount is in principle the maximum amount which can be addedas a ratio to the perfume in the form of the manufactured article.).

After supplying the demulsifying agent, stirring was continued for 10minutes. Thereafter, each one of the round-bottomed centrifuging tubes(inner diameter: 10 mm, depth: 80 mm) was charged with each liquidmixture in an amount of 6 g/tube, one liquid mixture per tube. Thecentrifugation was carried out with a centrifuge (commercially availablefrom Hitachi Koki Co., Ltd., trade name: “CR22G Rotor RPR18-3”) underconditions of 1000 rpm for one minute. Next, a liquid mixture wascollected from the central portion of the centrifuging tube in an amountof 0.35 mL per tube (collected at a position 30 mm above the deepestportion of the centrifuging tube. The emulsion is usually white-turbidand uniform. When demulsification takes place, a transparent layer isformed at the central portion by floating of a perfume, deposition of adegradation substance and the like, and this layer is collected. Whencollecting, careful attention should be paid so as not to collect thecomponents floating in the upper layer or the precipitated components inthe lower layer.). The absorbance of each collected liquid mixture wasdetermined with a UV meter (commercially available from ShimadzuCorporation, UV-1700) at 600 nm. The demulsification index wascalculated according to the following formula to judge the extent ofdemulsification. Those having a demulsification index of 0.3 or lesswere judged to be demulsified.Demulsification Index=((A−D)−(C−D))/(B−D)wherein:

-   A: absorbance when the above-mentioned procedures were carried out    with supplying a demulsifying agent to an emulsion;-   B: absorbance when the above-mentioned procedures were carried out    without supplying a demulsifying agent to an emulsion;-   C: absorbance when the above-mentioned procedures were carried out    with supplying a demulsifying agent to water; and-   D: absorbance when the above-mentioned procedures were carried out    without supplying a demulsifying agent to water (usually, 0).

The supplying amount of the demulsifying agent in the case of a laundrypowder detergent, which is one of the preferred embodiments of thepresent invention, will be illustrated hereinbelow. The judgment on thepresence or absence of demulsification in the Examples given below wascarried out on the basis of the following methods.

Evaluation 1: Demulsification with Protease

The amount 0.5 g of protease granules (“KAP13.1B” commercially availablefrom Kao Corporation, 13.1 APU/g based on the unit (APU) determined bythe method for determining the degradation activity againsturea-modified hemoglobin described in paragraph [0029] of JapanesePatent No. 2750789) was added (the manufactured article was assumed tocontain 0.05% by weight of a perfume and 0.5% by weight of “KAP13.1B”).

Evaluation 2: Demulsification with Cellulase

0.5 g of cellulase granules (“KAC-1500B” commercially available from KaoCorporation, 14000 KU/g based on the unit (KU) determined by the methodfor determining enzyme activity described in paragraph [0020] ofJapanese Patent Laid-Open No. Hei 10-313859) was added (the manufacturedarticle assumed to contain 0.05% by weight of a perfume and 0.5% byweight of “KAC-1500B”).

Evaluation 3: Demulsification with Alkali

0.03 g of sodium carbonate (“DENSE ASH” commercially available fromShikoku Kasei K.K.) was added (the manufactured article was assumed tocontain 0.05% by weight of a perfume and 30% by weight of “DENSE ASH”;however, the amount of the latter component was reduced since it is theconcentration (pH) that is believed to be important for the actionmechanism of an alkali.).

As an overall judgment, those having a calculated value according to theabove calculation formula of 0.3 or more in any one of the evaluationmethods was judged “negative”, and those having a calculated value ofless than 0.3 in any one of the evaluation methods was judged“positive.”

(Process for Preparing Perfume Particles)

A perfume, an emulsifying agent (emulsification active substance), amatrix-forming agent and water were each weighed in a ratio shown inTable 1 to make up a total amount of 4000 g. The components other thanthe perfume were placed into an 8 L vessel, and mixed at a rotationalspeed of 2000 r/m for 30 minutes by a laboratory homomixer (commerciallyavailable from Tokushu Kika Kogyo Co., Ltd., “ROBOMICS” (registeredtrade mark)) to dissolve the components. Next, the perfume was addedthereto, and the mixture was treated at 10000 r/m for 1 hour to form anemulsion. All emulsions were emulsions prepared by emulsifying into oildroplets having a size of about 2 μm, and were stable emulsions whichdid not cause any separation after allowing the emulsion to stand for 1hour. The resulting emulsion was fed to a spray-drying tower at a rateof 100 g/min, and microgranulated by a binary fluid nozzle, and dried byfeeding hot air of 120° C. The obtained dried product was separated andcollected with a cyclone. As a result, particles having an averageparticle size of about 50 μm were obtained. A SEM image of the crosssection of the perfume particle 6 is shown in FIG. 1.

(Detergent Base)

A powder detergent having the composition shown in Table 5 was used as ageneral laundry powder detergent (no-perfuming: having slight odors ofthe surfactant and enzyme).

(Direct Perfuming Method in Comparative Examples)

A perfume was sprayed onto the detergent composition (detergent base)shown in Table 5 with spray. Spraying and mixing were repeated, andperfuming was carried out until the intended amount was reached.

Comparative Examples 1 to 3, Examples 1 and 2

Each of the detergent compositions shown in Table 2 was obtained byusing perfume particles shown in Table 1. The odor of the detergentcomposition was evaluated in two stages; one is the odor of the powderdetergent itself, and the other is the fragrance of the cloth aftercompletion of washing, rinsing and spin-drying processes in a washingmachine (herein referred to as “spin-dried cloth” in some cases). It canbe seen from the results that the odor of the powder detergent itself issignificantly suppressed and that the dissipated amount of the perfumeis small in all cases using any perfume particles except for ComparativeExample 1. In addition, it can be seen that the compositions (Examples 1and 2) containing a combination to be demulsified according to thepresent invention efficiently release the fragrance of the perfumesformulated, without differing from that of the direct perfuming product,while the compositions being emulsified perfumes are excellent instorage stability, contrary to that the fragrance of the spin-driedcloth decreases in Comparative Examples 2 and 3.

Comparative Examples 4 and 5, Examples 3 and 4

The evaluation results when the kind of perfume was changed are shown inTable 3. In the direct perfuming products shown in Comparative Examples4 and 5, the fragrance is found to lower during storage, because ofdissipation in the case of limonene, which is a perfume of highvolatility, and degradation in the case of pentalide, which is a perfumeof lower alkali resistance. In contrast, in Examples 3 and 4 eachcontaining a combination of the perfume particles and the demulsifyingagent according to the present invention, the fragrance is unchangeablyexhibited on the spin-dried cloths after the storage of the detergentcompositions. Even in the case of perfumes which have beenconventionally difficult to use, the properties can be satisfactorilyexhibited. Therefore, it can be seen that the perfume composition of thepresent invention is also an excellent technique even in the aspect offlexibility of using different kinds of perfume.

Comparative Examples 6 to 9, Examples 5 and 6

The evaluation results when the direct perfuming is carried out to thecomposition of the present invention are shown in Table 4. It can beseen from the results that since the process for releasing perfume ofthe present invention is a process of efficiently releasing perfume uponuse while releasing only little perfume during storage, the fragrance ofthe spin-dried cloth (adsorption onto clothes) can be designed duringthe wash, without being limited by change of the odor of the powderdetergent itself. Therefore, it can be seen that the present inventionis a technique capable of designing a variety of perfume matching one'slife style by a combination with the properties (kind, volatility andthe like of perfume) of the perfume itself. TABLE 1 Perfume PerfumePerfume Perfume Perfume Perfume Particle 1 Particle 2 Particle 3Particle 4 Particle 5 Particle 6 Kind of Perfume Formulation A¹⁾Formulation A¹⁾ Formulation A¹⁾ Formulation A¹⁾ Formulation B³⁾Formulation C³⁾ Kind of Emulsifying Agent Gum Arabic²⁾ Lipophilic Nasalt of Cationated Cationated Cationated Starch³⁾ Casein⁴⁾ HydroxyethylHydroxyethyl Hydroxyethyl Cellulose Cellulose Cellulose Composition (%by wt.) Perfume 4 4 4 4 4 4 Emulsifying Agent 4 4 4 0.1 0.1 0.1Matrix-Forming Agent⁵⁾ 32 32 32 35.9 35.9 35.9 Water 60 60 60 60 60 60Total 100 100 100 100 100 100 Judgment of Emulsification⁶⁾ Emulsion (−)0.12 0.13 0.18 0.09 — — Evaluation 1: KAP (−) 1.8 1.1 0.0 0.0 — —Evaluation 2: KAC (−) 0.6 0.5 0.8 0.0 — — Evaluation 3: Alkali (−) 0.90.8 1.0 0.8 — — Overall Judgment Negative Negative Positive PositivePositive Positive¹⁾Formulated Perfume A: Floral-based formulated perfume (degree ofvolatilization: medium to low);²⁾Gum arabic: Reagent “gum arabic” commercially available from KishidaKagaku K.K.³⁾Perfume B: Limonene (orange-based, degree of volatilization: high);Perfume C: Pentalide (musk-based, degree of volatilization: low);Lipophilic Starch: commercially available from Matsutani Kagaku KogyoK.K. under the trade name of “Emulstar 30A”⁴⁾Na salt of Casein: commercially available from Saneigen FFI K.K. underthe trade name of “Casein Natrium”⁵⁾Matrix-Forming Agent: Maltodextrin (Matsutani Kagaku Kogyo K.K. underthe trade name of “Pinedex #2”)⁶⁾Judgment made by the method for judging demulsification in detergent(those having negative calculated values were considered as 0.)Cationated Hydroxyethyl Cellulose: commercially available from KaoCorporation under the trade name of “POISE C-80M”

TABLE 2 Comp. Comp. Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 1 Ex. 2 Kind DetergentDeter- Deter- Deter- Deter- Deter- Base Material gent gent gent gentgent Base Base Base Base Base Perfume — Perfume Perfume Perfume PerfumeParticles Parti- Parti- Parti- Parti- cle 1 cle 2 cle 3 cle 4 Kind ofPerfume Formula- — — — — for Direct tion A Perfuming Amount Perfumed (asPerfume) Perfume Particles 0.045 0.045 0.045 0.045 (% by weight, ratioto detergent base material) Direct Perfuming 0.045 — — — — (% by weight,ratio to detergent base material) Strength of Fragrance¹⁾ Odor of Powder3.0 1.0 1.0 1.0 1.0 Detergent Fragrance of 3.0 1.3 1.7 3.3 3.0Spin-Dried Cloth¹⁾Strength of Fragrance: On the basis of Comparative Example 1, thosehaving notably stronger fragrance were ranked 1, those having slighterstronger fragrance were ranked 4, those having equivalent fragrance wereranked 3, and those having a weaker fragrance were ranked 2, and thosehaving notably weaker fragrance were ranked 1, and an average of threespecialist panelists were taken.Since the test was a sensory evaluation in each state, those having thesame evaluation numerals do not necessarily coincide in the strength ofthe fragrance between the detergent powder and the spin-dried cloth.

TABLE 3 Comp. Comp. Ex. 4 Ex. 3 Ex. 5 Ex. 4 Kind Detergent BaseDetergent Detergent Detergent Detergent Material Base Base Base BasePerfume Particles — Perfume — Perfume Particle 5 Particle 6 Kind ofPerfume for Limonene — Pentalide — Direct Perfuming Amount Perfumed (asPerfume) Perfume Particles — 0.2 — 0.2 (% by weight, ratio to detergentbase material) Direct Perfuming 0.2 — 0.2 — (% by weight, ratio todetergent base material) Strength of Fragrance Before Storage Odor ofPowder 3.0 1.3 3.0 1.0 Detergent Fragrance of 3.0 3.3 3.0 3.0 Spin-DriedCloth Strength of Fragrance After Storage Odor of Powder 2.0 1.0 2.0 1.0Detergent Fragrance of 1.3 3.0 1.0 2.7 Spin-Dried ClothComp. Ex. 4, and Ex. 3: Evaluated on the basis of before the storage ofComp. Ex. 4;Comp. Ex. 5, and Ex. 4: Evaluated on the basis of before the storage ofComp. Ex. 5;Storage Conditions: 50° C. for 2 weeks in a bottle with a lid withslight aeration.Since the test was a sensory evaluation in each state, those having thesame evaluation numerals do not necessarily coincide in the strength ofthe fragrance between the detergent powder and the spin-dried cloth.

TABLE 4 Comp. Ex. 6 Comp. Ex. 7 Ex. 5 Comp. Ex. 8 Comp. Ex. 9 Ex. 6 KindDetergent Base Material Detergent Detergent Detergent DetergentDetergent Detergent Base Base Base Base Base Base Perfume Particles — —Perfume — — Perfume Particle 4 Particle 5 Kind of Perfume forFormulation A Formulation A Formulation A Formulation A Formulation AFormulation A Direct Perfuming 1 Kind of Perfume for — — — — Limonene —Direct Perfuming 2 Amount Perfumed (as Perfume) Perfume Particles — —0.35 — — 1.00 (% by weight, ratio to detergent base material) DirectPerfuming 1 0.35 0.70 0.35 0.20 0.20 0.20 (% by weight, ratio todetergent base material) Direct Perfuming 2 — — — — 1.00 — (% by weight,ratio to detergent base material) Strength of Fragrance¹⁾ Odor of PowderDetergent Appropriately Notably Strong Appropriately AppropriatelyNotably Appropriately Floral Floral Floral Floral Strong Citrus FloralFragrance During Washing Slightly Slightly Strong Slightly StrongSlightly Appropriately Appropriately Floral Floral Floral Floral CitrusCitrus Fragrance of Spin-Dried Cloth Very Little AppropriatelyAppropriately Very Little Slightly Slightly Floral Floral Floral FloralCitrus CitrusOrder of Strength of Fragrance: Notably strong > slightly strong >appropriately > slightly > very little

TABLE 5 LAS 13% by weight Nonionic Surfactant 13% by weight SodiumCarbonate 20% by weight Sodium Sulfate 15% by weight Zeolite 30% byweight Protease Granules¹⁾ 0.3% by weight Cellulase Granules²⁾ 0.2% byweight Others³⁾ 8.5% by weight Total 100.0% by weight¹⁾commercially available from Kao Corporation under the trade name of“KAP13.1B”;²⁾commercially available from Kao Corporation under the trade name of“KAC-1500B”;³⁾others: dispersants, fluorescent whitening agents and the like.

The present invention being thus described, it will be obvious that thesame may be varied in many ways. Such variations are not to be regardedas a departure from the spirit and scope of the invention, and all suchmodifications as would be obvious to one skilled in the art are intendedto be included within the scope of the following claims.

1. A process for releasing fragrance comprising the step of treating a)a perfume emulsified with one or more substances having emulsificationactions, with b) a demulsifying agent capable of demulsifying at leastone of the substances having emulsification actions.
 2. The processaccording to claim 1, wherein the demulsifying agent is at least onemember selected from the group consisting of enzymes, alkalis, acids,electrolytes, and mixtures thereof.
 3. A perfume composition comprising:a) a perfume emulsified with one or more substances havingemulsification actions, and b) a demulsifying agent capable ofdemulsifying at least one of the substances having emulsificationactions.
 4. The perfume composition according to claim 3, wherein thedemulsifying agent is at least one member selected from the groupconsisting of enzymes, alkalis, acids, electrolytes, and mixturesthereof.
 5. A detergent composition comprising the perfume compositionof claim
 3. 6. The detergent composition according to claim 5, furthercomprising one or more members selected from the group consisting ofsurfactants, alkalizing agents, water softening agents, polymers,enzymes, and mixtures thereof.
 7. A process for preparing a detergentcomposition comprising carrying out direct perfuming to the perfumecomposition of claim
 3. 8. A process for preparing a detergentcomposition comprising carrying out direct perfuming to the detergentcomposition of claim 5.